WO2019057627A1 - Compositions d'esters d'acide polyaspartique et procédé de purification - Google Patents

Compositions d'esters d'acide polyaspartique et procédé de purification Download PDF

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Publication number
WO2019057627A1
WO2019057627A1 PCT/EP2018/074885 EP2018074885W WO2019057627A1 WO 2019057627 A1 WO2019057627 A1 WO 2019057627A1 EP 2018074885 W EP2018074885 W EP 2018074885W WO 2019057627 A1 WO2019057627 A1 WO 2019057627A1
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Prior art keywords
polyaspartic
general formula
acid ester
purified
polyaspartic acid
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PCT/EP2018/074885
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German (de)
English (en)
Inventor
Dorota Greszta-Franz
Christian Drumm
Jan MORBACH
Reiner Witkowski
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Covestro Deutschland Ag
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Priority to CN201880060623.4A priority Critical patent/CN111065620A/zh
Priority to US16/648,366 priority patent/US10968165B2/en
Priority to EP18765668.1A priority patent/EP3849962A1/fr
Publication of WO2019057627A1 publication Critical patent/WO2019057627A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/38—Separation; Purification; Stabilisation; Use of additives
    • C07C227/40—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers

Definitions

  • the present invention relates to a process for the purification of polyaspartic ester compositions and the provision of polyaspartic esters containing 0.01 to ⁇ 2 wt.% Fumarcic aciddialkylester.
  • Polyaspartic acid esters are used in two-component coating compositions which contain a polyisocyanate component as binder. Such coating compositions are suitable for the production of high-quality coatings which can be adjusted to be hard, elastic, resistant to abrasion and solvents.
  • An advantage over primary amines is the moderate reactivity of the amine functions contained in the polyaspartic esters over isocyanates.
  • EP0403921, EP0639628, EP0667362, EP0689881, US5,214,086, US6,605,684, EP0573860, EP0699696, EP0596360, EP0893458, DE19701835, DE102006002153, EP1767559, WO2001007504, WO2001007399, WO2004033517, US6458293, EP1426397 and US5,243,012 describe by way of example low-viscosity polyaspartic esters, which secondary
  • polyaspartic esters are also called aspartates and are particularly suitable for producing low-solvent or -amideer coating compositions which show rapid curing.
  • the reaction of maleic or fumaric acid esters with primary amines is carried out using ratios such that each primary amino group has at least one and preferably exactly one olefinic double bond.
  • an undesired secondary reaction may take place in which dialkyl fumarate (dialkyl fumarate) is formed as a secondary component.
  • dialkyl fumarate dialkyl fumarate
  • a typical manufacturing process of a polyaspartic acid ester requires a storage time of 4-6 weeks after most of the reactants have reacted with each other. During this time, the so-called maturation of the product, which manifests itself by stabilizing the viscosity occurs.
  • dialkyl fumarate Due to the fact that sales continue to increase within this time, the content of dialkyl fumarate also decreases. This storage over several weeks leads to significant logistics costs within the production. Furthermore, although the product is only after storage delivered to customers, it still contains substantial amounts of dialkyl fumarate which can cause sensitization. After completion of the reaction, polyaspartic esters thus prepared usually contain residues of from 3 to 20% by weight of unreacted fumaric and / or maleic acid esters.
  • fumaric and / or maleic acid esters can be separated by distillation. Conditions under which the separation can be carried out successfully, does not name the document.
  • DE102006002153A1 likewise describes the preparation of aspartic acid esters which contain several percent by weight of diethyl fumarate as raw material, but also after storage.
  • Example 3 it is mentioned that the excess diethyl fumarate was completely removed by thin film distillation. Again, the required distillation conditions are not discussed.
  • this document describes positive technical effects of a content of 2 to 10% by weight of diethyl fumarate in the aspartic acid ester, such as low viscosity coupled with good pot life and final hardness, it should be noted that such a high diethyl fumarate content may also be present has the above-mentioned adverse effects.
  • polyaspartic esters having less than 2 percent by weight of free dialkyl fumarates.
  • a content of less than 0.01% by weight brings here no further advantage in terms of processing conditions and can be realized technically only with considerable effort.
  • the object of the present invention is to provide a method for purifying polyaspartic ester compositions for providing polyaspartic esters which can be easily applied in common applications with minimal health risk.
  • This process should be particularly suitable for those polyaspartic esters which have a low platinum-cobalt color number. This problem could be solved by the inventive method for the purification of
  • Polyaspartic acid ester compositions for providing purified polyaspartic acid esters containing ⁇ 2% by weight fumaric acid dialkyl ester.
  • the present invention relates to a process for purifying polyaspartic ester compositions comprising polyaspartic esters of the general formula (I)
  • X is an m-valent, optionally one or more
  • Heteroatom-containing organic radical is, as it can be obtained by removal of primary amino groups from a corresponding, aromatic, (cyclo) aliphatic or araliphatically bound primary amino groups having polyamine in the molecular weight range 60 to 6000 g / mol, and the other isocyanate-reactive and / or may contain inert functional groups at temperatures up to 100 ° C,
  • R 1 and R 2 represent the same or different organic radicals each having 1 to 18
  • Carbon atoms, m is an integer> 1, characterized in that the purified polyaspartic acid ester contains from 0.01 to ⁇ 2 wt.% Fumarcic aciddialkylester.
  • a preferred object of the present invention is the above-mentioned process for purifying polyaspartic ester compositions of the general formula (I) in which
  • X is an m-valent organic radical optionally containing one or more heteroatoms, as obtained by removal of primary amino groups from polyetherpolyamines having aliphatically bonded primary amino groups, 1,2-diaminopropane, 1,4-diaminobutane, 1,5-
  • Diaminodicyclohexylmethane or 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane is obtained,
  • R 1 and R 2 represent identical or different alkyl radicals each having 1 to 8 carbon atoms
  • n is an integer> 1, characterized in that the purified polyaspartic acid ester contains a proportion of 0.01-0.2% by weight of fumaric acid dialkyl ester.
  • a further preferred subject matter of the present invention is the abovementioned process for purifying polyaspartic ester compositions comprising polyaspartic esters of the general formula (I),
  • X is an m-valent organic radical, as obtained by removal of primary amino groups from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 2,4'- and / or 4,4'-diaminodicyclohexylmethane, 1 , 5-diamino-2-methylpentane can be obtained
  • R 1 and R 2 represent identical or different alkyl radicals selected from the group
  • m is 2, characterized in that the purified polyaspartic acid ester contains a proportion of 0.01 to 0.2 percent by weight of fumaric acid dialkyl ester.
  • Another preferred object of the present invention is the above-mentioned process for purifying polyaspartic ester compositions containing polyaspartic acid esters of the general formula (I) in which
  • X is an m-valent organic radical, as can be obtained by removal of primary amino groups from 2,4 'and / or 4,4'-diaminodicyclohexylmethane, R 1 and R 2 are ethyl radicals,
  • a further subject matter of the present invention is a process for purifying polyaspartic ester compositions comprising polyaspartic esters of the general formula (I)
  • X is an m-valent, optionally containing one or more heteroatoms organic radical, as he by removal of primary amino groups from a corresponding, aromatic, (cyclo) aliphatic or araliphatic bound primary amino groups having polyamine in the molecular weight range 60 to 6000 g / mol and which may contain further isocyanate-reactive and / or inert at temperatures up to 100 ° C functional groups,
  • R 1 and R 2 represent the same or different organic radicals each having 1 to 18
  • a polyaspartic ester composition comprising polyaspartic acid esters of the general formula (I) and purified in at least one further step, characterized in that the purified polyaspartic ester contains from 0.01 to ⁇ 2% by weight of fumaric acid dialkyl ester.
  • a preferred object of the present invention is the above-mentioned process for purifying polyaspartic ester compositions of the general formula (I) in which
  • X is an m-valent organic radical optionally containing one or more heteroatoms, as obtained by removal of primary
  • Amino groups of polyether polyamines having aliphatically bonded primary amino groups 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,5-diamino-2-methylpentane, 2,5-diamino-2, 5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1, 6-diaminohexane, 1,11-diaminounodecane, 1,12-diaminododecane, 1-amino
  • Diaminodicyclohexylmethane or 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane is obtained,
  • R 1 and R 2 represent identical or different alkyl radicals each having 1 to 8 carbon atoms
  • a further preferred subject matter of the present invention is the abovementioned process for purifying polyaspartic ester compositions comprising polyaspartic esters of the general formula (I), is an m-valent organic radical, as obtained by removal of primary amino groups from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 2,4- and / or 4,4'-diaminodicyclohexylmethane, 1.5 - Diamino-2-methylpentane can be obtained
  • a polyaspartic ester composition comprising polyaspartic esters of the general formula (I) be reacted and purified in a further step, characterized in that the purified polyaspartic acid ester contains a proportion of 0.01 to 0.2 percent by weight Fumarkladialkylester.
  • a further preferred subject matter of the present invention is the abovementioned process for purifying polyaspartic ester compositions comprising polyaspartic esters of the general formula (I),
  • X is an m-valent organic radical, as can be obtained by removal of primary amino groups from 2,4'- and / or 4,4'-diaminodicyclohexylmethane,
  • R 1 and R 2 are ethyl radicals
  • m is 2, characterized in that substituted maleic and / or fumaric acid esters of the general formula (II), wherein the radicals Rl and R2 have the abovementioned meanings, with primary polyamines of the general formula (III), wherein X and m have the meanings mentioned above, to a polyaspartic acid ester composition containing polyaspartic acid ester of the general formula (I) and purified in a further step, characterized in that the purified polyaspartic ester contains a proportion of 0.01 to 0.1 percent by weight of fumaric acid dialkyl ester.
  • maleic and / or Fumarkladialkylester of formula (II) are used in which for Rl and R2 are identical or different alkyl radicals each having 1 to 18 carbon atoms, preferably identical or different alkyl radicals each having 1 to 8 carbon atoms and all particularly preferred for each alkyl radicals such as methyl, ethyl, propyl, iso-propyl, butyl or iso-butyl radicals. Particularly preferred is diethyl maleate.
  • diesters may be mentioned for compounds of the general formula (II): dimethyl maleate, diethyl ester, di-n-butyl ester, the corresponding fumaric acid esters or the corresponding methyl-substituted in the 2- and / or 3-position Maleic acid or fumaric acid ester.
  • Polyamines of the general formula (III) which can be used for the process according to the invention are selected from the following group: all known polyamines having primary amino groups which correspond to the general formula (III).
  • the following compounds may be mentioned by way of example: ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 2,5-diamino-2,5-dimethylhexane, 1,5-diamino-2-methylpentane (Dytek ®A, Fa DuPont), 1,6-diaminohexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,1-diaminoundecane, 1,1-diaminododecane or triaminononane , Etheramines, such as 4,9-dioxadodecane-l, 12-diamine, 4,7,
  • Tricyclodecanbismethylamine (TCD-diamine) or bis (aminomethyl) norbornane, amino-functional siloxanes, e.g. Diaminopropylsiloxane G10 DAS (from Momentive), fatty alkyl based amines, e.g. Fentamine from Solvay, dimer fatty acid diamines such as priamines from Croda.
  • TCD-diamine Tricyclodecanbismethylamine
  • amino-functional siloxanes e.g. Diaminopropylsiloxane G10 DAS (from Momentive)
  • fatty alkyl based amines e.g. Fentamine from Solvay
  • dimer fatty acid diamines such as priamines from Croda.
  • polyamines of the general formula (III) selected from the group consisting of polyether polyamines having aliphatically bonded primary amino groups, 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane,
  • Diamino-dicyclohexylmethane or 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane is particularly preferred.
  • polyamines of the general formula (III) selected from the group: 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 2,4- and / or 4,4'-diaminodicyclohexylmethane, 1 , 5-diamino-2-methylpentane and very particularly preferred is the use of 2,4- and / or 4,4'-diaminodicyclohexylmethane.
  • aromatic polyamines such as 2,4- and / or 2,6-diaminotoluene or 2,4'- and / or 4,4'-diaminodiphenylmethane or their polynuclear homologues.
  • relatively high molecular weight polyether polyamines having aliphatically bonded primary amino groups such as those sold under the name Jeffamine®.
  • m is an integer> 1 and preferably 2.
  • polyaspartic acid ester composition containing polyaspartic acid ester of the general formula (I) can be stored or matured for several weeks and / or worked up by the inventive method for purification.
  • Polyaspartic acid ester compositions contain from 70 to 98% by weight, preferably from 80 to 98% by weight and more preferably from 85 to 98% by weight of polyaspartic acid ester of the general formula (I).
  • the purified polyaspartic acid ester is the product which is obtained by the process according to the invention for purifying polyaspartic ester compositions comprising polyaspartic acid esters of the general formula (I). It preferably contains from 0.01 to ⁇ 2 wt.%, Preferably 0.01 to 0.2 wt.% And particularly preferably 0.01 to 0.1 wt.% Fumarkladialkylester.
  • purified polyaspartic esters which have a platinum-cobalt color number ⁇ 100, preferably ⁇ 50 and particularly preferably ⁇ 30, and a proportion of 0.01 to ⁇ 2 wt.%, preferably 0.01 to 0.2 wt.% and particularly preferably 0.01 to 0.1 wt.% of fumaric acid dialkyl ester.
  • Another object of the present invention is the above-mentioned method of purification, characterized in that containing polyaspartic acid ester compositions
  • Polyaspartic acid ester of the general formula (I) with a platinum-cobalt color number ⁇ 100 are purified.
  • purified polyaspartic esters for coatings it is preferred if they have a platinum cobalt color number ⁇ 100, more preferably ⁇ 50.
  • the measurement of the platinum-cobalt color number is carried out in accordance with DIN EN ISO 6271: 2016-05.
  • formula (I) is not to be expected, so that preference is given to purifying those polyaspartic ester compositions comprising polyaspartic esters of the general formula (I) by the process according to the invention which already have a platinum-cobalt color number ⁇ 100, preferably ⁇ 50 and more preferably ⁇ 30 have.
  • Another object of the present invention is the above-mentioned method for purification, wherein the polyaspartic acid ester compositions containing polyaspartic acid ester of the general formula (I) are purified by distillation.
  • Another object of the present invention is the above-mentioned method for
  • polyaspartic ester compositions containing polyaspartic acid ester of the general formula (I) are purified by distillation at a pressure below 20 mbar and a temperature below 180 ° C.
  • Another object of the present invention is the above-mentioned method for purification, wherein the polyaspartic acid ester compositions comprising polyaspartic acid ester of the general formula (I) is purified by distillation, characterized in that
  • distillation is carried out at a pressure between 0.005 and 2 mbar and
  • the distillation is carried out at a pressure between 0.005 and 2 mbar, preferably between 0.005 and 0.8 mbar, more preferably between 0.005 and 0.2 mbar.
  • Another object of the present invention is the above-mentioned method for purification, characterized in that the time during which the polyaspartic acid ester composition containing polyaspartic acid ester of the general formula (I), is exposed to temperatures above 100 ° C, less than 2 hours. In a further preferred embodiment, therefore, the time during which the
  • Polyaspartic acid ester compositions containing polyaspartic esters of the general formula (I) exposed to temperatures above 100 ° C are limited to less than 2 hours, preferably less than 30 minutes, more preferably less than 10 minutes.
  • Another object of the present invention is the abovementioned process for purification, characterized in that the bottom effluent comprising the purified polyaspartic acid ester is cooled directly after leaving the distillation apparatus to temperatures below 100 ° C, wherein the average residence time of the bottom effluent between exit from the distillation apparatus and entering a cooler below 5 minutes.
  • the bottoms effluent is therefore cooled directly after leaving the distillation apparatus to temperatures below 100 ° C, preferably below 80 ° C.
  • "directly after leaving the distillation apparatus” is understood to mean that the mean residence time of the bottoms effluent between exit from the distillation apparatus and entry into a cooler is less than 5 minutes, preferably less than 2 minutes and particularly preferably less than 1 minute.
  • At least the last stage of the distillation is characterized by the conditions given above.
  • Suitable apparatuses for the distillation according to the invention are, for example, falling-film evaporators, thin-film evaporators and / or short-path evaporators. Preference is given to the use of thin film evaporators and / or short path evaporators, since these allow a particularly gentle distillation.
  • Another object of the present invention is the above-mentioned method for purification, characterized in that the distillation is carried out using falling film evaporator, thin film evaporator and / or short path evaporator.
  • Another object of the present invention is the above-mentioned method for purification, characterized in that the distillation in two stages using a Combination of thin-film evaporator and subsequent short-path evaporator is performed.
  • the distillation is carried out in two stages, that is, in two connected in series evaporators wherein the purified polyaspartic ester is obtained in each case at the bottom of the evaporator.
  • a further subject of the present invention are polyaspartic ester compositions containing compounds of the general formula (I)
  • X is an m-valent, optionally one or more
  • Heteroatom-containing organic radical as obtained by removal of primary amino groups from a corresponding, aromatic, (cyclo) aliphatic or araliphatically bonded primary amino groups containing polyamine in the molecular weight range 60 to 6000 g / mol, and the other, reactive toward isocyanate groups and / or may contain inert functional groups at temperatures up to 100 ° C,
  • R 1 and R 2 represent the same or different organic radicals each having 1 to 18
  • Another object of the present invention are polyaspartic acid ester compositions containing compounds of general formula (I), in which
  • X is an m-valent organic radical optionally containing one or more heteroatoms, as obtained by removal of primary
  • Amino groups of polyether polyamines having aliphatically bonded primary amino groups 1,2 diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, l, 5-diamino-2-methylpentane, 2.5 diamino-2.5 dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminounodecane, 1,12-diaminododecane, 1-amino-
  • R 1 and R 2 represent identical or different alkyl radicals each having 1 to 8 carbon atoms
  • a further subject of the present invention are polyaspartic ester compositions containing compounds of the general formula (I) in which X is an m-valent organic radical, as obtained by removal of primary amino groups from 3,3'-dimethyl-4,4 ' diamino-dicyclohexylmethane, 2,4- and / or 4,4'-diaminodicyclohexylmethane, 1,5-diamino-2-methylpentane can be obtained,
  • R 1 and R 2 represent identical or different alkyl radicals selected from the group
  • m is 2, characterized in that a proportion of 0.01-0.2% by weight of fumaric acid dialkyl ester is contained and a platinum Cobalt color number ⁇ 30 is present.
  • Another object of the present invention are polyaspartic acid ester compositions containing compounds of general formula (I), in which X is an m-valent organic radical, as can be obtained by removal of primary amino groups from 2,4- and / or 4,4'-diaminodicyclohexylmethane,
  • R 1 and R 2 are ethyl radicals
  • m 2 characterized in that a proportion of 0.01 to 0.1 wt.% Fumarcicredialkylester is present and a platinum-cobalt color number ⁇ 30 is present.
  • the starting substance was tetraethyl-N, N '- (methylenedicyclohexane-4, l-diyl) bis-DL-aspartate (CAS No. 136210-30-5) which had a platinum-cobalt color number of 15 and a content of
  • the quantitative determination of the content of diethyl fumarate in the samples was carried out by means of a GC method with an internal standard.
  • a GC Agilent with a fused silica capillary and a FID detector was used.
  • the temperature of the injector (split outlet) was 180 ° C, helium was used as the carrier gas.
  • the limit of quantification of this method was 300 ppm.
  • Polyaspartic acid ester A was first purified by distillation, so that the content of
  • Fumaric acid dialkyl ester (FADE) in the purified polyaspartic acid ester was 0.07% by weight. Samples of this purified polyaspartic acid ester were then annealed at 70 ° C, at 100 ° C and at 130 ° C. At the beginning and after 2 h and after 5 h, the annealed samples were examined for their content of FADE. The results of the heat treatment are summarized in the following Table 1. The percentages are each weight percent of FADE in the sample.
  • Example 2 200 kg of the polyaspartic acid ester A are distilled as in Example 2. Now, however, the bottom effluent is passed directly after leaving the evaporator in a heat exchanger and cooled there to 70 ° C, before the product is stored for storage in a steel container. After 2 hours, a sample is examined for its content of FADE. This is 0.07 wt.
  • Percent and the platinum-cobalt color number of the sample is 30.
  • Example 3 200 kg of the polyaspartic acid ester A are distilled as in Example 3, with the difference that this time a pressure of 1 mbar is set. A sample of the stored product is examined after 2 hours for its content of FADE. This is 0.7 percent by weight and the platinum-cobalt color number of the sample is 28.
  • Example 2 Cooling of the sump drain. In contrast to Example 2, this time a pressure of 0.5 mbar is set and the heating power is increased, so that the temperature of the bottom outlet is 175 ° C.
  • the sample after 2 h has a FADE content of 0.37% by weight.
  • a discoloration of the product shows.
  • the platinum-cobalt color number is 240.

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Abstract

La présente invention concerne un procédé de purification de compositions d'esters d'acide polyaspartique et la préparation d'esters d'acide polyaspartique contenant de 0,01 à < 2 % en poids de dialkylester d'acide fumarique.
PCT/EP2018/074885 2017-09-19 2018-09-14 Compositions d'esters d'acide polyaspartique et procédé de purification WO2019057627A1 (fr)

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CN201880060623.4A CN111065620A (zh) 2017-09-19 2018-09-14 多天冬氨酸酯组合物和提纯方法
US16/648,366 US10968165B2 (en) 2017-09-19 2018-09-14 Polyaspartic acid ester compositions and method for purification
EP18765668.1A EP3849962A1 (fr) 2017-09-19 2018-09-14 Compositions d'esters d'acide polyaspartique et procédé de purification

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EP17191793.3 2017-09-19
EP17191793.3A EP3456706A1 (fr) 2017-09-19 2017-09-19 Compositions d'esters d'acide polyaspartique et procédé de nettoyage

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EP4137524A1 (fr) 2021-08-17 2023-02-22 Covestro Deutschland AG Nouveaux systèmes de revêtement à deux composants contenant des esters d'acide polyasparagique

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* Cited by examiner, † Cited by third party
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CN113544182B (zh) * 2019-03-19 2023-09-19 科思创知识产权两合公司 基于环醚的含仲氨基的粘料

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB573154A (en) 1942-06-26 1945-11-08 American Cyanamid Co Improvements in or relating to n-substituted aspartic acid esters and methods of preparing same
EP0403921A2 (fr) 1989-06-23 1990-12-27 Bayer Ag Procédé pour la préparation de revêtements
US5214086A (en) 1991-09-04 1993-05-25 Basf Corporation Coating compositions which may be ambient cured
US5243012A (en) 1992-06-10 1993-09-07 Miles Inc. Polyurea coating compositions having improved pot lives
EP0596360A1 (fr) 1992-11-06 1994-05-11 Bayer Ag Composés d'alcoxysilanes contenant des groupes amino
EP0639628A1 (fr) 1993-08-19 1995-02-22 Bayer Ag Procédé de production de revêtements
EP0667362A1 (fr) 1994-02-09 1995-08-16 Bayer Corporation Compositions de polyurée pour revêtement à entreposage prolongé
EP0689881A1 (fr) 1994-05-05 1996-01-03 Bayer Ag Procédé de fabrication des couches
EP0699696A1 (fr) 1994-08-29 1996-03-06 Bayer Corporation Mélanges de polyisocyanate et polyamines et leur utilisation dans la production de vernis à base de polyurée
EP0816326A1 (fr) * 1996-07-02 1998-01-07 Bayer Ag Procédé de préparation d'esters d'acide mono- ou polyaspartique
DE19701835A1 (de) 1997-01-21 1998-07-23 Huels Chemische Werke Ag Kalthärtende, lösemittelarme oder lösemittelfreie Zweikomponenten-Polyurethan-Polyharnstoff-Massen
EP0893458A1 (fr) 1997-07-23 1999-01-27 Herberts Gesellschaft mit beschränkter Haftung Agents de revêtement et leur utilisation dans des procédés de revêtement multi-couche
WO2001007399A1 (fr) 1999-07-23 2001-02-01 Bayer Corporation Preparation in situ d'un melange d'ester polyaspartique
WO2001007504A1 (fr) 1999-07-23 2001-02-01 Bayer Corporation Preparation in situ d'un melange d'esters polyaspartiques
US6458293B1 (en) 1999-07-29 2002-10-01 Bayer Corporation Polyurea coatings from dimethyl-substituted polyaspartic ester mixtures
US6605684B2 (en) 1997-03-11 2003-08-12 Huntsman Petrochemical Corporation Method of preparing spray elastomer systems
WO2004033517A1 (fr) 2002-10-07 2004-04-22 Bayer Materialscience Ag Systemes a deux constituants permettant la production de revetements elastiques
EP1426397A1 (fr) 2002-12-05 2004-06-09 Bayer Polymers LLC Resine de polyaspartate avec bonne dureté et flexibilité
EP1767559A1 (fr) 2005-09-22 2007-03-28 The Hanson Group, LLC Procédé de préparation de polymères polyurée et leurs utilisation
DE102006002153A1 (de) 2006-01-17 2007-07-19 Bayer Materialscience Ag Polyasparaginsäureester-haltige Bindemittel
US20090191145A1 (en) 2008-01-24 2009-07-30 Bayer Materialscience Ag Adhesive systems containing polyisocyanate prepolymers and aspartate-ester curing agents, processes for preparing the same, medical uses therefor and dispensing systems for the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6737500B1 (en) * 1999-07-23 2004-05-18 Bayer Polymers Llc In-situ preparation of polyaspartic ester mixture
US6774207B2 (en) * 2002-09-26 2004-08-10 Bayer Polymers Llc Polyaspartate resins with good hardness and flexibility
US6984715B2 (en) * 2003-10-03 2006-01-10 Bayer Materialscience Llc Process for preparing aspartates
CN101024618B (zh) * 2007-02-12 2010-08-18 江苏省化工研究所有限公司 一种天门冬氨酸酯的制备方法
CN107805207B (zh) * 2017-10-18 2020-01-31 万华化学集团股份有限公司 一种聚天门冬氨酸酯的制备方法

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB573154A (en) 1942-06-26 1945-11-08 American Cyanamid Co Improvements in or relating to n-substituted aspartic acid esters and methods of preparing same
EP0403921A2 (fr) 1989-06-23 1990-12-27 Bayer Ag Procédé pour la préparation de revêtements
US5214086A (en) 1991-09-04 1993-05-25 Basf Corporation Coating compositions which may be ambient cured
US5243012A (en) 1992-06-10 1993-09-07 Miles Inc. Polyurea coating compositions having improved pot lives
EP0573860A1 (fr) 1992-06-10 1993-12-15 Bayer Corporation Compositions de revêtement de polyurée stables à l'entreposage
EP0596360A1 (fr) 1992-11-06 1994-05-11 Bayer Ag Composés d'alcoxysilanes contenant des groupes amino
EP0639628A1 (fr) 1993-08-19 1995-02-22 Bayer Ag Procédé de production de revêtements
EP0667362A1 (fr) 1994-02-09 1995-08-16 Bayer Corporation Compositions de polyurée pour revêtement à entreposage prolongé
EP0689881A1 (fr) 1994-05-05 1996-01-03 Bayer Ag Procédé de fabrication des couches
EP0699696A1 (fr) 1994-08-29 1996-03-06 Bayer Corporation Mélanges de polyisocyanate et polyamines et leur utilisation dans la production de vernis à base de polyurée
EP0816326A1 (fr) * 1996-07-02 1998-01-07 Bayer Ag Procédé de préparation d'esters d'acide mono- ou polyaspartique
DE19701835A1 (de) 1997-01-21 1998-07-23 Huels Chemische Werke Ag Kalthärtende, lösemittelarme oder lösemittelfreie Zweikomponenten-Polyurethan-Polyharnstoff-Massen
US6605684B2 (en) 1997-03-11 2003-08-12 Huntsman Petrochemical Corporation Method of preparing spray elastomer systems
EP0893458A1 (fr) 1997-07-23 1999-01-27 Herberts Gesellschaft mit beschränkter Haftung Agents de revêtement et leur utilisation dans des procédés de revêtement multi-couche
WO2001007399A1 (fr) 1999-07-23 2001-02-01 Bayer Corporation Preparation in situ d'un melange d'ester polyaspartique
WO2001007504A1 (fr) 1999-07-23 2001-02-01 Bayer Corporation Preparation in situ d'un melange d'esters polyaspartiques
US6458293B1 (en) 1999-07-29 2002-10-01 Bayer Corporation Polyurea coatings from dimethyl-substituted polyaspartic ester mixtures
WO2004033517A1 (fr) 2002-10-07 2004-04-22 Bayer Materialscience Ag Systemes a deux constituants permettant la production de revetements elastiques
EP1426397A1 (fr) 2002-12-05 2004-06-09 Bayer Polymers LLC Resine de polyaspartate avec bonne dureté et flexibilité
EP1767559A1 (fr) 2005-09-22 2007-03-28 The Hanson Group, LLC Procédé de préparation de polymères polyurée et leurs utilisation
DE102006002153A1 (de) 2006-01-17 2007-07-19 Bayer Materialscience Ag Polyasparaginsäureester-haltige Bindemittel
US20090191145A1 (en) 2008-01-24 2009-07-30 Bayer Materialscience Ag Adhesive systems containing polyisocyanate prepolymers and aspartate-ester curing agents, processes for preparing the same, medical uses therefor and dispensing systems for the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAUBEN WEYL, METH. D. ORG. CHEMIE, vol. 11/1, 1957, pages 272

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4137524A1 (fr) 2021-08-17 2023-02-22 Covestro Deutschland AG Nouveaux systèmes de revêtement à deux composants contenant des esters d'acide polyasparagique
WO2023020960A1 (fr) 2021-08-17 2023-02-23 Covestro Deutschland Ag Nouveaux systèmes de revêtement à deux composants contenant des esters d'acide polyaspartique

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